CN112940370A - Submarine cable filling hard profile and forming process thereof - Google Patents
Submarine cable filling hard profile and forming process thereof Download PDFInfo
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- CN112940370A CN112940370A CN202110116722.3A CN202110116722A CN112940370A CN 112940370 A CN112940370 A CN 112940370A CN 202110116722 A CN202110116722 A CN 202110116722A CN 112940370 A CN112940370 A CN 112940370A
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- section bar
- submarine cable
- cable filling
- profile
- matrix resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/06—Rod-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The application particularly discloses a submarine cable filling hard section bar and a forming process thereof. The submarine cable filling hard section bar is formed by polymerizing the following raw materials in parts by weight: 40-60 parts of elastomer hard filler; 30-50 parts of matrix resin; 0.1-0.5 part of reinforcing agent; 0.2-1 part of a stabilizer; 0.5-1.5 parts of a coupling agent; 1-3 parts of an anti-aging agent. The molding process comprises the following steps: heating, stirring and melting elastomer hard filler and matrix resin, adding the remaining four raw materials, and stirring to obtain a section bar melt; placing the section bar melt under the temperature control of the five sections, and performing extrusion molding by using a rubber extruder to obtain a section bar initial sample; step (3) placing the profile initial sample in a three-section temperature control mode, and stretching the profile initial sample at a stretching machine to obtain a profile; and (4) rolling the section bar. The submarine cable filling hard profile can be used for filling submarine cables, and the surface of the submarine cable filling hard profile is smooth, flat and elastic; in addition, the forming process has a stretching and reinforcing effect on the section bar, so that the elasticity and the strength of the section bar are higher.
Description
Technical Field
The application relates to the technical field of submarine cable fillers, in particular to a submarine cable filling hard profile and a forming process thereof.
Background
With the development of ocean wind power and national economy, the demand on submarine cables is increased, and the requirements on the working reliability and environmental protection performance are increased.
The conventional submarine cable is generally filled with polypropylene reticular tear ropes at the voltage level of 35kV or below, and the voltage level above 35kV is large in cable core outer diameter and large in gap after cabling, and the polypropylene reticular tear ropes are difficult to ensure the roundness of the submarine cable, so that the voltage level above 35kV is mostly in a molding filling strip structure, and the conventional filling strip for the submarine cable is mostly subjected to material return secondary processing, so that the surface is not smooth, the unit weight is large, resources are wasted, the manufacturing cost is increased, and the requirement of the development strategy of the national environment-friendly type is not met.
The existing submarine cable filling strip is not smooth enough in surface after molding and not enough in elasticity, and in the submarine cable laying and using process, the protection on a cable core is not uniform enough, so that the quality hidden danger is caused, and the long-term operation working reliability of the submarine cable filling strip is reduced.
Disclosure of Invention
In order to improve the surface smoothness and elasticity of the filling strip, the application provides a submarine cable filling hard profile and a forming process thereof.
In a first aspect, the present application provides a submarine cable filling hard profile, which adopts the following technical scheme:
the submarine cable filling hard section bar is prepared by polymerizing the following raw materials in parts by weight:
by adopting the technical scheme, the elastomer hard filler and the matrix resin are used as main raw materials for molding the section bar, and after the elastomer hard filler and the matrix resin are melted and mixed, the matrix resin has an adhesion effect on the elastomer hard filler, so that the molded section bar has higher structural strength and smooth surface, and the elastomer hard filler enables the molded section bar to have elasticity; the reinforcing agent can improve the tensile strength, the wear resistance, the tearing strength and the stress at definite elongation of the section bar, improve the service performance of the section bar and prolong the service life; the stabilizer can promote the vulcanization of the section bar, increase the vulcanization degree of the section bar, enable the section bar to be filled in the submarine cable, and the submarine cable is not easy to break during laying, improve the elasticity and tensile strength of the section bar, and further facilitate the stretching of the section bar; the coupling agent is a substance with two functional groups with different properties, namely an inorganophilic group and an organophilic group, so that organic molecules and inorganic molecules are combined more tightly in the molding process of the profile, the interface action between the inorganic molecules and the organic molecules is improved, and the elasticity and the surface strength of the profile are improved; the anti-aging agent can delay aging of the high molecular compound, inhibit oxidation and inhibit the high molecular compound from aging under the action of heat, oxygen and valence-variable metal ions, and further improve the service durability of the section bar when the section bar is placed in a submarine cable for filling after being formed.
Preferably, the elastomeric hard filler is ground particles of tires having 5 to 40 mesh.
By adopting the technical scheme, the tire crushing particles are used, the effect of recycling the tire can be achieved, the environment is protected, the tire is crushed to 5-40 meshes, and the tire particles are convenient to melt.
Preferably, the matrix resin is any one or a combination of more of high density polyethylene, linear low density polyethylene and polystyrene.
By adopting the technical scheme, the high-density polyethylene can improve the hardness, tensile strength and wear resistance of the section bar, and the high-density polyethylene has good chemical stability; the linear low-density polyethylene has high strength, good toughness and good cold resistance, and after the linear low-density polyethylene is used as a raw material to prepare the section bar, the section bar can resist the low-temperature environment of the seabed and is not easy to crack when in actual use; the polystyrene can be insulated, has good processing fluidity, can improve the insulating property of the section bar after being used as a section bar raw material to prepare the section bar, and is convenient to process.
Preferably, the matrix resin comprises high density polyethylene and linear low density polyethylene, and the mixing ratio of the high density polyethylene to the linear low density polyethylene is 1: (0.5-1).
By adopting the technical scheme, the high-density polyethylene and the linear low-density polyethylene are compounded for use, and the formed section bar has good strength, good toughness and excellent tensile strength.
Preferably, the reinforcing agent is carbon black.
By adopting the technical scheme, the surface activity of the carbon black particles is not uniform, and the surfaces of the carbon black particles have a few strong active points and a large number of adsorption points with different energies, so that the carbon black particles have different binding energies to molecular chains, and can be most of adsorption caused by van der waals force or few chemical binding bonds. When the molding strip is subjected to an external force, the adsorbed molecular chains slide and extend on the surface of the carbon black particles, and then a reinforcing effect is generated.
Preferably, the stabilizer is an organotin stabilizer.
Preferably, the coupling agent is an aluminate coupling agent.
Preferably, the anti-aging agent is formed by compounding an anti-aging agent AP and an anti-aging agent MB, and the weight part mixing ratio of the anti-aging agent AP to the anti-aging agent MB is 1: (0.7-1).
By adopting the technical scheme, the anti-aging agent AP is 3-carboxyl butyraldehyde-alpha-naphthylamine and has good thermal oxidation resistance, so that the molding strip is inhibited from being oxidized by heating in the molding process, and the anti-aging agent MB is 2-mercaptobenzimidazole and has good anti-aging performance when being compounded with the anti-aging agent AP for use.
In a second aspect, the present application provides a molding process for filling a hard profile for a submarine cable, which adopts the following technical scheme:
a molding process of a submarine cable filling hard profile comprises the following steps:
placing elastomer hard filler and matrix resin at the temperature of 100-110 ℃, stirring at the speed of 10-20r/min until the elastomer hard filler and the matrix resin are molten, adding reinforcing agent, stabilizer, coupling agent and anti-aging agent, and stirring at the speed of 20-30r/min for 10-15min to obtain bar melt;
step (2) placing the section bar melt material in the step (1) at a rubber extruder, and adopting five-section temperature control, wherein the temperature is controlled in a preheating zone of 110-;
step (3) placing the shaped bar initial sample in the step (2) at the temperature of 100-130 ℃, and stretching in a stretching machine to obtain a shaped bar;
and (4) rolling the section bar in the step (3) by using a rolling disc.
By adopting the technical scheme, in the step (1), the elastomer hard filler and the matrix resin are mixed, heated and melted, then stirred to ensure that the elastomer hard filler and the matrix resin are uniformly distributed in a molten state, the reinforcing agent, the stabilizing agent, the coupling agent and the anti-aging agent are added to modify the section bar raw material in the molten state, and the four additives are more uniformly distributed in the section bar raw material by stirring; in the step (2), when the section bar melt is molded, five-section temperature control is adopted, the section bar melt is preheated in a preheating zone, the heated softening zone heats and softens the section bar melt, so that the section bar melt is heated and internally mixed in a first internal mixing zone and a second internal mixing zone, the section bar melt is preliminarily molded in a molding zone and is extruded from a rubber extruder at a lower speed, so that the section bar primary sample is not easy to break, and the five-section temperature control is adopted, so that the section bar melt is slowly heated and heated; in the step (3), placing the initial sample of the section bar at a stretching machine for heating and stretching to ensure that the section bar is subjected to stretching plasticity; and (4) rolling the profile after the drawing and forming.
Preferably, three temperature controls are adopted in the step (3), wherein the temperature control includes a heating zone of 110-.
By adopting the technical scheme, three-stage temperature control is adopted in the step (3), so that the temperature of the profile initial sample can be slowly increased in the heating and softening process, and the difference between the surface property and the internal property of the profile initial sample caused by the fact that the surface temperature of the profile initial sample is increased too fast is reduced; the profile is first appearance and preheats in the zone of heating, softens at softening tensile district and stretches, carries out preliminary cooling shaping in the shaping district, at the forming process, takes place the shrink between the profile molecular chain, and then has improved the structural strength and the ageing resistance performance of profile, and the surface is more smooth.
In summary, the present application has the following beneficial effects:
1. the section bar is formed by polymerizing the following raw materials in parts by weight: 40-60 parts of elastomer hard filler; 30-50 parts of matrix resin; 0.1-0.5 part of reinforcing agent; 0.2-1 part of a stabilizer; 0.5-1.5 parts of a coupling agent; 1-3 parts of anti-aging agent, wherein elastomer hard filler and matrix resin are used as main raw materials for molding the section bar, and after the elastomer hard filler and the matrix resin are melted and mixed, the matrix resin has an adhesion effect on the elastomer hard filler, so that the molded section bar has higher structural strength and smooth surface, and the elastomer hard filler enables the molded section bar to have elasticity; the reinforcing agent can improve the tensile strength, the wear resistance, the tearing strength and the stress at definite elongation of the section bar, improve the service performance of the section bar and prolong the service life; the stabilizer can promote the vulcanization of the section bar, increase the vulcanization degree of the section bar, enable the section bar to be filled in the submarine cable, and the submarine cable is not easy to break during laying, improve the elasticity and tensile strength of the section bar, and further facilitate the stretching of the section bar; the coupling agent is a substance with two functional groups with different properties, namely an inorganophilic group and an organophilic group, so that organic molecules and inorganic molecules are combined more tightly in the molding process of the profile, the interface action between the inorganic molecules and the organic molecules is improved, and the elasticity and the surface strength of the profile are improved; the anti-aging agent can delay aging of the high molecular compound, inhibit oxidation and inhibit the high molecular compound from aging under the action of heat, oxygen and valence-variable metal ions, and further improve the service durability of the section bar when the section bar is placed in a submarine cable for filling after being formed.
2. The method comprises the following four steps: placing elastomer hard filler and matrix resin at the temperature of 100-110 ℃, stirring at the speed of 10-20r/min until the elastomer hard filler and the matrix resin are molten, adding reinforcing agent, stabilizer, coupling agent and anti-aging agent, and stirring at the speed of 20-30r/min for 10-15min to obtain bar melt; step (2) placing the section bar melt material in the step (1) at a rubber extruder, and adopting five-section temperature control, wherein the temperature is controlled in a preheating zone of 110-; step (3) placing the shaped bar initial sample in the step (2) at the temperature of 100-130 ℃, and stretching in a stretching machine to obtain a shaped bar; and (4) rolling the section bar in the step (3) by using a rolling disc. In the step (1), after the elastomer hard filler and the matrix resin are mixed, heated and melted, the elastomer hard filler and the matrix resin are stirred to be uniformly distributed in a molten state, and after the reinforcing agent, the stabilizing agent, the coupling agent and the anti-aging agent are added, the reinforcing agent, the stabilizing agent, the coupling agent and the anti-aging agent play a role in modifying the section bar raw material in the molten state, and the four additives are stirred to be more uniformly distributed in the section bar raw material; in the step (2), when the section bar melt is molded, five-section temperature control is adopted, the section bar melt is preheated in a preheating zone, the heated softening zone heats and softens the section bar melt, so that the section bar melt is heated and internally mixed in a first internal mixing zone and a second internal mixing zone, the section bar melt is preliminarily molded in a molding zone and is extruded from a rubber extruder at a lower speed, so that the section bar primary sample is not easy to break, and the five-section temperature control is adopted, so that the section bar melt is slowly heated and heated; in the step (3), placing the initial sample of the section bar at a stretching machine for heating and stretching to ensure that the section bar is subjected to stretching plasticity; and (4) rolling the profile after the drawing and forming.
3. The method adopts three-stage temperature control in the step (3), wherein the heating zone is 110-; the profile is first appearance and preheats in the zone of heating, softens at softening tensile district and stretches, carries out preliminary cooling shaping in the shaping district, at the forming process, takes place the shrink between the profile molecular chain, and then has improved the structural strength and the ageing resistance performance of profile, and the surface is more smooth.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
Examples
Examples 1 to 9
Table 1 part by weight ratio of each raw material in the submarine cable filling rigid profiles according to examples 1 to 8 of the present application
In the raw materials for filling the hard profile of the submarine cable in the above examples 1 to 8, the elastomer hard filler is crushed particles of tires of 5 to 40 meshes, the reinforcing agent is carbon black, the stabilizer is an organic tin stabilizer, and the coupling agent is an aluminate coupling agent.
The preparation method of the submarine cable filling hard profile in the above embodiments 1 to 8 includes the following steps:
placing elastomer hard filler and matrix resin at 110 ℃, stirring the elastomer hard filler and the matrix resin by using a stirrer at the rotating speed of 15r/min until the elastomer hard filler and the matrix resin are molten, simultaneously adding reinforcing agent, stabilizer, coupling agent and anti-aging agent, and stirring for 15min at the rotating speed of 25r/min by using the stirrer to obtain a molding bar melt;
placing the section bar melt material in the step (1) at a rubber extruder, enabling the section bar melt material to respectively pass through a preheating zone at 120 ℃, a melting zone at 150 ℃, a first-section banburying zone at 160 ℃, a second-section banburying zone at 180 ℃ and a sampling zone at 160 ℃, and extruding the section bar melt material from the rubber extruder at the speed of 15m/min to obtain a section bar initial sample;
step (3) placing the profile blank sample obtained in the step (2) at a stretching machine for stretching, so that the profile blank sample respectively passes through a heating zone at 115 ℃, a softening stretching zone at 125 ℃ and a forming zone at 105 ℃ to obtain a profile;
and (4) rolling the section bar in the step (3) by using a rolling disc.
Example 9
Example 9 differs from example 3 in that step (3) of the preparation method of example 9 is: and (3) placing the initial section bar sample in the step (2) at a stretching machine, and stretching at the temperature of 120 ℃ to obtain the section bar.
Comparative example
Comparative examples 1 to 3
TABLE 2 part ratio by weight of each raw material in the submarine cable filling rigid profiles of comparative examples 1 to 3 in this application
In the raw materials for filling the hard profile of the submarine cable in the comparative examples 1 to 3, the elastomer hard filler is crushed particles of tires of 5 to 40 meshes, the reinforcing agent is carbon black, the stabilizer is an organic tin stabilizer, and the coupling agent is an aluminate coupling agent.
The preparation method of the submarine cable filling hard profile in comparative examples 1 to 3 comprises the following steps:
placing elastomer hard filler and matrix resin at 110 ℃, stirring the elastomer hard filler and the matrix resin by using a stirrer at the rotating speed of 15r/min until the elastomer hard filler and the matrix resin are molten, simultaneously adding reinforcing agent, stabilizer, coupling agent and anti-aging agent, and stirring for 15min at the rotating speed of 25r/min by using the stirrer to obtain a molding bar melt;
placing the section bar melt material in the step (1) at a rubber extruder, enabling the section bar melt material to respectively pass through a preheating zone at 120 ℃, a melting zone at 150 ℃, a first-section banburying zone at 160 ℃, a second-section banburying zone at 180 ℃ and a sampling zone at 160 ℃, and extruding the section bar melt material from the rubber extruder at the speed of 15m/min to obtain a section bar initial sample;
step (3) placing the profile blank sample obtained in the step (2) at a stretching machine for stretching, so that the profile blank sample respectively passes through a heating zone at 115 ℃, a softening stretching zone at 125 ℃ and a forming zone at 105 ℃ to obtain a profile;
and (4) rolling the section bar in the step (3) by using a rolling disc.
Performance test
Detection method
The appearance test, the tensile strength test, the tensile elongation test and the aging property test were conducted for examples 1 to 9 and comparative examples 1 to 3, respectively. Wherein, the detection method in GB/T1040-92 is adopted for the tensile strength detection and the tensile elongation detection, and the detection method in GB7141-8 is adopted for the aging performance detection.
The data of the performance test on the submarine cable-filled rigid profiles of examples 1 to 9 and comparative examples 1 to 3 are shown in table 3.
Table 3 data of performance test of submarine cable filled rigid profiles in examples 1 to 9 and comparative examples 1 to 3
As can be seen by combining examples 1-2 in Table 1 and the performance test data of examples 1-2 in Table 3, the profiles in examples 1-2 have smooth surfaces, good tensile strength and tensile elongation, and good tensile strength after aging test.
When high density polyethylene and linear low density polyethylene were used as a compounding resin for the matrix resin, the tensile strength and tensile elongation of the molded bars after molding were significantly increased, as can be seen by combining examples 1 to 2 and example 8 in table 1 with the performance test data of examples 1 to 3 and example 8 in table 3.
When the antioxidant is compounded by using the antioxidant AP and the antioxidant MB, it can be seen from the combination of example 3 in Table 1 and comparative examples 1 to 3 in Table 2 and the performance test data of example 3 and comparative examples 1 to 3 in Table 3 that the molded bars have better aging resistance.
When the mixing ratio of the high density polyethylene and the linear low density polyethylene in parts by weight in the matrix resin is 1: (0.5-1), the formed profile has better tensile strength and tensile elongation; when the weight part mixing ratio of the antioxidant AP to the antioxidant MB in the antioxidant is 1: (0.7-1), the molded molding has better aging resistance.
By combining example 3 and example 9 in table 1 and by combining the performance test data of example 3 and example 9 in table 3, it can be seen that when three-stage temperature control is not adopted in step (3) of the molding process, the molded profile surface is not smooth enough, the tensile strength and tensile elongation performance indexes are both significantly reduced, and the aging resistance is also reduced.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The submarine cable filling hard profile is characterized by comprising the following raw materials in parts by weight:
2. a submarine cable filling rigid profile according to claim 1, wherein: the elastomer hard filler is crushed particles of tires with 5-40 meshes.
3. A submarine cable filling rigid profile according to claim 1, wherein: the matrix resin is any one or a combination of more of high-density polyethylene, linear low-density polyethylene and polystyrene.
4. A submarine cable filling rigid profile according to claim 3, wherein: the matrix resin comprises high-density polyethylene and linear low-density polyethylene, and the mixing ratio of the high-density polyethylene to the linear low-density polyethylene in parts by weight is 1: (0.5-1).
5. A submarine cable filling rigid profile according to claim 1, wherein: the reinforcing agent is carbon black.
6. A submarine cable filling rigid profile according to claim 1, wherein: the stabilizer is an organic tin stabilizer.
7. A submarine cable filling rigid profile according to claim 1, wherein: the coupling agent is an aluminate coupling agent.
8. A submarine cable filling rigid profile according to claim 1, wherein: the anti-aging agent is formed by compounding an anti-aging agent AP and an anti-aging agent MB, and the weight part mixing ratio of the anti-aging agent AP to the anti-aging agent MB is 1: (0.7-1).
9. A process for forming a submarine cable filled rigid profile according to any one of claims 1 to 8, comprising the steps of:
placing elastomer hard filler and matrix resin at the temperature of 100-110 ℃, stirring at the speed of 10-20r/min until the elastomer hard filler and the matrix resin are molten, adding reinforcing agent, stabilizer, coupling agent and anti-aging agent, and stirring at the speed of 20-30r/min for 10-15min to obtain bar melt;
step (2) placing the section bar melt material in the step (1) at a rubber extruder, and adopting five-section temperature control, wherein the temperature is controlled in a preheating zone of 110-;
step (3) placing the shaped bar initial sample in the step (2) at the temperature of 100-130 ℃, and stretching in a stretching machine to obtain a shaped bar;
and (4) rolling the section bar in the step (3) by using a rolling disc.
10. The process for forming a submarine cable filled rigid profile according to claim 9, wherein: in the step (3), three-stage temperature control is adopted, wherein the temperature is respectively controlled by a heating zone of 110-.
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